CN109395607A - A kind of polytetrafluoroethylene film and preparation method thereof - Google Patents
A kind of polytetrafluoroethylene film and preparation method thereof Download PDFInfo
- Publication number
- CN109395607A CN109395607A CN201710712542.5A CN201710712542A CN109395607A CN 109395607 A CN109395607 A CN 109395607A CN 201710712542 A CN201710712542 A CN 201710712542A CN 109395607 A CN109395607 A CN 109395607A
- Authority
- CN
- China
- Prior art keywords
- stem
- transforaminal
- hole
- porosity
- area
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/36—Polytetrafluoroethene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/364—Membrane distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0004—Organic membrane manufacture by agglomeration of particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/06—Flat membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/39—Electrospinning
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/04—Characteristic thickness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The present invention provides a kind of polytetrafluoroethylene films, have the pore structure of three-dimensional perforation, there is transforaminal on the stem of hole, and hole aperture is 200 ± 100nm, and stem diameter is 125 ± 25nm, 45 ± 25nm of transforaminal aperture；Wherein the porosity of hole is 60 ± 10%, and the porosity of transforaminal is 55 ± 10%；The total surface area of the stem, stem area: transforaminal area=15-30:1；Film thickness is greater than 10 μm.The polytetrafluoroethylene film that the present invention provides a kind of service phases is long, antifouling property is excellent.
Description
Technical field
The present invention relates to polytetrafluoroethylene films and preparation method thereof to be particularly suitable for membrane distillation for separating.
Technical background
Polytetrafluoroethylene (PTFE) since its use temperature range is wide, while have excellent chemical stability, low frictional properties and absolutely
Edge thermal insulation not only has excellent chemical stability, thermal stability, electricity using the separation membrane material that polytetrafluoroethylene (PTFE) is prepared as raw material
Insulating properties also has the characteristics such as outstanding waterproof, radix saposhnikoviae, moisture-inhibiting, ventilative and charge stable storing.It is in manufacture protective garment, bag
Formula deduster, architectural lighting etc. have shown excellent performance.National Palaestra " Bird Nest ", dome in thousand of Britain etc.
A large amount of PTFE microporous barriers are used.However that there are still flux in the application is small, filtering essence for current microporous teflon membran
The disadvantages of low, fenestra is easy to pollute, at high cost is spent, the application of industrialized production is had not been achievable.
Inventor has been devoted to the research to the structure of high molecular material, and the control and modification to material structure can get
The high molecular material of different characteristics and function.However polytetrafluoroethylene film relation be- tween structure and properties are not made clear of at present
It is thorough, as separation accuracy is difficult to take into account with treatment effeciency；With accurate microstructure, it is easy to impaired, service phase is short, use cost
It is high；Polytetrafluoroethylene (PTFE) physical and chemical performance is stablized, and structure control, performance improvement realize difficulty is big, and difficulty of processing is big etc.；Polytetrafluoroethyl-ne
Alkene material is in separation in application, how to cooperate with matching to obtain better performance etc. between microstructure and macroscopic form.
Summary of the invention
The polytetrafluoroethylene film that the purpose of the present invention is to provide a kind of service phases is long, antifouling property is excellent.
The purpose of the present invention is what is realized by following measures:
A kind of polytetrafluoroethylene film has the pore structure of three-dimensional perforation, there is transforaminal, hole aperture on the stem of hole
For 200 ± 100nm, stem diameter is 125 ± 75nm, 45 ± 25nm of transforaminal aperture；Wherein the porosity of hole is 60 ± 10%, stem
The porosity in hole is 55 ± 10%；The total surface area of the stem, stem area: transforaminal area=15-30:1；Film thickness is greater than 10 μm.
The film is during the Selective Separation for substance, when one such or different kinds of molecules is passing through material table
When face and/or inside, the microstructure of molecule will receive itself and the effect of material and the influence of bond structure, to affect object
The percent of pass and throughput of matter, the microstructure of another aspect material also will receive influence, to influence material separation tower, clothes
Labour phase etc..So both ensure that separate substance by efficiency and throughput, combine the utilization rate of material.Transforaminal is on stem
Distribution situation be one of key factor.
Preferably, in order to further increase correlated performance, the polytetrafluoroethylene film, hole aperture is 150-
250nm, stem diameter 100-120nm, transforaminal aperture 25-50nm；Wherein the porosity of hole is 55-65%, the porosity of transforaminal
For 50-55%；The total surface area of the stem, stem area: transforaminal area=20-26:1.
Preferably, 100-300 μm of above-mentioned film thickness.
Polytetrafluoroethylene (PTFE) has stable inert physical and chemical performance, and processing is not easy, especially for its microstructure
Control and holding are even more industry problem.The present invention provides the preparation method of the polytetrafluoroethylene film of above-mentioned special construction,
Using method of electrostatic spinning, including the preparation of spinning lotion, spinning, preforming, sintering, temperature-control pressure-control continuous sintering in the sintering；
It is described it is preforming be that the precursor film for obtaining spinning is wrapped on cylinder branch hold mode and forms plate morphology；Winding circle number is controllably film-made
It is thick.
The present invention provides the preparation method with the PTFE high molecular material of above structure, comprising the following steps:
(1) spinning solution prepares: polytetrafluoroethylene (PTFE) is added in the polyvinyl alcohol homogeneous solution soluble in water for obtaining 14-15% concentration
(PTFE) lotion (55-60%), so that PTFE and polyvinyl alcohol mass ratio are 2-3:1；
(2) spinning: electrostatic spinning is carried out using high-voltage electrostatic spinning apparatus, obtains even fiber precursor film；Spinning voltage
15 ~ 20kV, 12 ~ 30cm of distance；
(3) preforming: the precursor film that spinning is obtained is wrapped on cylinder branch hold mode and forms plate morphology；
(4) be sintered: 1. under a high vacuum (3-5Pa) with 5-6 DEG C/min from room temperature to 98-103 DEG C, and keep temperature and
Pressure 25-30min；2. being filled with nitrogen in 60-150s to pressure 65-70kpa, while temperature value is warming up to 4-5 DEG C/min
Be not more than 385 DEG C greater than 380 DEG C, and 65-70kpa, greater than 380 DEG C no more than keeping 8-12min at 385 DEG C；3. heating knot
Keep vacuum to cooling to 50-100Pa.
It is thick according to winding circle numerical control film in preforming step.Gained film after cooling is cut off as plate membrane.
Above-mentioned spinning lotion is prepared as preparing high molecular polymerization composition granule, the high molecular polymer using emulsion polymerization
Grain average grain diameter is 15-80nm.This makes material have better stem, pore size, optimizes the property such as impact flexibility, ageing resistance
Energy.
Porosity=hole porosity of material+(porosity of 1- hole) * transforaminal porosity.
Beneficial effect
1. the present invention improves the treating capacity that material carries out substance selection by the improvement to polytetrafluoroethylene (PTFE) semi-permeable material structure
With the persistence of selection separating property, the selection separative efficiency and selection effect of material are good, and the service phase of material is long.
2. the super-hydrophobic polytetrafluoroethylfiber fiber film that the present invention is coupled hardness with softness has stable and firm fibre morphology
With transforaminal structure, collapsing for bone skeleton is prevented.
3. stain resistance of the present invention is strong, the permanently effective operation of energy；Under the same operating conditions, the cleaning frequency is longer.
Specific embodiment
The present invention is specifically described below by embodiment, it is necessary to which indicated herein is that the present embodiment can only be used
In invention is further explained, it should not be understood as limiting the scope of the invention, the people that is skilled in technique in the field
Member can make some nonessential modifications and adaptations according to the content of aforementioned present invention.
Embodiment 1
A kind of polytetrafluoroethylene film has the pore structure of three-dimensional perforation, there is transforaminal, hole aperture on the stem of hole
For 200 ± 100nm, stem diameter is 125 ± 75nm, 45 ± 25nm of transforaminal aperture；Wherein the porosity of hole is 60 ± 10%, stem
The porosity in hole is 55 ± 10%；The total surface area of the stem, stem area: transforaminal area=15-30:1.100-300 μm of film thickness.
Stem surface area graphical analysis: with scanning electron microscope (SEM photograph amplifies 10000-50000 times) shooting material
Photo.The photo (the TV image processor TVIP- of Japanese Avionics company production is scanned with image processing facility
The TV image processor that 4100II, Latock system engineering company provide) stem and transforaminal are separated to obtain stem and transforaminal figure
As handling image by software, obtaining respective area, stem area and transforaminal area-graph can be calculated as the ratio between gross area.
Aperture, stem diameter, porosity are detected using nanometer CT.
The preparation method of this polytetrafluoroethylene film, according to the following steps:
(1) spinning solution prepares: polytetrafluoroethylene (PTFE) is added in the polyvinyl alcohol homogeneous solution soluble in water for obtaining 14-15% concentration
(PTFE) lotion (55-60%), so that PTFE and polyvinyl alcohol mass ratio are 2-3:1；
(2) spinning: electrostatic spinning is carried out using high-voltage electrostatic spinning apparatus, obtains even fiber precursor film；Spinning voltage
15 ~ 20kV, 12 ~ 30cm of distance；
(3) preforming: the precursor film that spinning is obtained is wrapped on cylinder branch hold mode and forms plate morphology；
(4) be sintered: 1. under a high vacuum (3-5Pa) with 5-6 DEG C/min from room temperature to 98-103 DEG C, and keep temperature and
Pressure 25-30min；2. being filled with nitrogen in 60-150s to pressure 65-70kpa, while temperature value is warming up to 4-5 DEG C/min
Be not more than 385 DEG C greater than 380 DEG C, and 65-70kpa, greater than 380 DEG C no more than keeping 8-12min at 385 DEG C；3. heating knot
Keep vacuum to cooling to 50-100Pa.
160-170 ° of resulting materials hydrophobic angle.Gained PTFE material is carried out to taurine waste water membrane distillation at normal temperature, is had
Be adapted to industrial excellent properties and effect.Taurine can obtain the product better than the drug standards, and water reaches medical
Water for injection standard.Flux of membrane distillation > 20L/m2H, rejection stablize 99% or more, be carried out continuously membrane distillation 5 months with
On, flux drops to former flux 70-75%, and material color is pure white after cleaning, and flux recovery is before 95% or more, service phase
It is 3-5.
Embodiment 2
A kind of polytetrafluoroethylene film has the pore structure of three-dimensional perforation, there is transforaminal, hole aperture on the stem of hole
For 150-250nm, stem diameter 100-120nm, transforaminal aperture 25-50nm；Wherein the porosity of hole is 55-65%, transforaminal
Porosity is 50-55%；The total surface area of the stem, stem area: transforaminal area=20-26:1.120-150 μm of film thickness.
162-170 ° of resulting materials hydrophobic angle.Gained PTFE material is carried out to taurine waste water membrane distillation at normal temperature, is had
Be adapted to industrial excellent properties and effect.Taurine can obtain the product better than the drug standards, and water reaches medical
Water for injection standard.Flux of membrane distillation > 20L/m2H, rejection stablize 99% or more, be carried out continuously membrane distillation 5 months with
On, flux drops to former flux 70-75%, and material color is pure white after cleaning, and flux recovery is before 95% or more, service phase
It is 3-5.
Embodiment 3
A kind of polytetrafluoroethylene film has the pore structure of three-dimensional perforation, there is transforaminal, hole aperture on the stem of hole
For 230nm, stem diameter 110nm, transforaminal aperture 35nm；Wherein the porosity of hole is 62%, and the porosity of transforaminal is 52%；Institute
The total surface area of stem is stated, stem area: transforaminal area=24:1.120 μm of film thickness.
168 ° of resulting materials hydrophobic angle.Gained PTFE material is carried out to taurine waste water membrane distillation at normal temperature, is had suitable
It should be in industrial excellent properties and effect.Taurine can obtain the product better than the drug standards, and water reaches medical injection
Water supply standard.Flux of membrane distillation > 20L/m2H, rejection are stablized 99% or more, are carried out continuously membrane distillation 5 months or more, lead to
Amount drops to former flux 70-75%, and material color is pure white after cleaning, and before 95% or more, service phase can be grown flux recovery
Up to 3-5.
Claims (5)
1. a kind of polytetrafluoroethylene film has the pore structure of three-dimensional perforation, there is transforaminal, hole lyriform pore on the stem of hole
Diameter is 200 ± 100nm, and stem diameter is 125 ± 75nm, 45 ± 25nm of transforaminal aperture；Wherein the porosity of hole is 60 ± 10%,
The porosity of transforaminal is 55 ± 10%；The total surface area of the stem, stem area: transforaminal area=15-30:1；Film thickness is greater than 10 μm.
2. polytetrafluoroethylene film as described in claim 1, hole aperture is 150-250nm, stem diameter 100-120nm,
Transforaminal aperture 25-50nm；Wherein the porosity of hole is 55-65%, and the porosity of transforaminal is 50-55%；The total surface of the stem
Product, stem area: transforaminal area=20-26:1.
3. polytetrafluoroethylene film as claimed in claim 1 or 2,100-300 μm of film thickness.
4. the preparation method of polytetrafluoroethylene film as described in claim 1-3, using method of electrostatic spinning, including spinning lotion
Preparation, spinning, preforming, sintering, temperature-control pressure-control continuous sintering in the sintering.
5. the preparation method of polytetrafluoroethylene film as claimed in claim 6, it is described it is preforming be the forerunner for obtaining spinning
Film is wrapped on cylinder branch hold mode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710712542.5A CN109395607A (en) | 2017-08-18 | 2017-08-18 | A kind of polytetrafluoroethylene film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710712542.5A CN109395607A (en) | 2017-08-18 | 2017-08-18 | A kind of polytetrafluoroethylene film and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109395607A true CN109395607A (en) | 2019-03-01 |
Family
ID=65463053
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710712542.5A Pending CN109395607A (en) | 2017-08-18 | 2017-08-18 | A kind of polytetrafluoroethylene film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109395607A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101918488A (en) * | 2007-12-20 | 2010-12-15 | 菲利普莫里斯生产公司 | Hollow/porous fibers and applications thereof |
| CN103894077A (en) * | 2014-04-10 | 2014-07-02 | 江南大学 | Composite filter membrane with multidimensional pore structure and preparation method thereof |
| KR20150079209A (en) * | 2013-12-31 | 2015-07-08 | 도레이케미칼 주식회사 | Controlled surface porosity PTFE hollow-fiber type membrane and method for manufacturing thereof |
| CN104998557A (en) * | 2014-04-22 | 2015-10-28 | 成都百途医药科技有限公司 | Production method of super-hydrophobic polytetrafluoroethylene membrane |
| CN106669451A (en) * | 2015-11-11 | 2017-05-17 | 重庆润泽医药有限公司 | Polytetrafluoroethylene ultrafine fiber membrane |
| CN106669443A (en) * | 2015-11-11 | 2017-05-17 | 重庆润泽医药有限公司 | Polytetrafluoroethylene fiber tubular film |
| CN106948164A (en) * | 2017-03-08 | 2017-07-14 | 杭州安诺过滤器材有限公司 | Film being made up of the acid fiber by polylactic of the continuous poriferous structure of nanometer and preparation method thereof |
-
2017
- 2017-08-18 CN CN201710712542.5A patent/CN109395607A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101918488A (en) * | 2007-12-20 | 2010-12-15 | 菲利普莫里斯生产公司 | Hollow/porous fibers and applications thereof |
| KR20150079209A (en) * | 2013-12-31 | 2015-07-08 | 도레이케미칼 주식회사 | Controlled surface porosity PTFE hollow-fiber type membrane and method for manufacturing thereof |
| CN103894077A (en) * | 2014-04-10 | 2014-07-02 | 江南大学 | Composite filter membrane with multidimensional pore structure and preparation method thereof |
| CN104998557A (en) * | 2014-04-22 | 2015-10-28 | 成都百途医药科技有限公司 | Production method of super-hydrophobic polytetrafluoroethylene membrane |
| CN106669451A (en) * | 2015-11-11 | 2017-05-17 | 重庆润泽医药有限公司 | Polytetrafluoroethylene ultrafine fiber membrane |
| CN106669443A (en) * | 2015-11-11 | 2017-05-17 | 重庆润泽医药有限公司 | Polytetrafluoroethylene fiber tubular film |
| CN106948164A (en) * | 2017-03-08 | 2017-07-14 | 杭州安诺过滤器材有限公司 | Film being made up of the acid fiber by polylactic of the continuous poriferous structure of nanometer and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Prince et al. | Effect of hydrophobic surface modifying macromolecules on differently produced PVDF membranes for direct contact membrane distillation | |
| JP6567595B2 (en) | Method for producing a porous membrane | |
| Patel et al. | Synthesis of poly (vinyl chloride)-g-poly (3-sulfopropyl methacrylate) graft copolymers and their use in pressure retarded osmosis (PRO) membranes | |
| CN104812842A (en) | Polymer resin composition for producing microfiltration membrane or ultrafiltration membrane, production method for polymer filtration membrane, and polymer filtration membrane | |
| CN102649028A (en) | Hydrophobic separation membrane and preparation method | |
| CN102773024A (en) | Method for preparing hollow fiber type forward osmotic membrane | |
| CN105749769A (en) | Preparation method and application of ionic liquid blended membrane | |
| Li et al. | Biologically inspired silk fibroin grafted polyacrylonitrile filtration membrane prepared in ZnCl2 aqueous solution | |
| Liu et al. | A hydrophobic pervaporation membrane with hierarchical microporosity for high-efficient dehydration of alcohols | |
| CN107020019B (en) | A kind of ultra-fine polyvinylidene fluoride hollow fiber dry state film of high throughput and preparation method thereof | |
| CN109395607A (en) | A kind of polytetrafluoroethylene film and preparation method thereof | |
| KR20170100851A (en) | Porous support for water treatment membrane, thin-film composite membrane containing the same and preparation method thereof | |
| CN109395615A (en) | A kind of polytetrafluoroethylene film and preparation method thereof | |
| CN109088086A (en) | Compound non-porous proton exchange membrane of a kind of nano-cellulose enhancing and preparation method thereof | |
| KR20120118408A (en) | Membrane, method for manufacturing the same and forward osmosis device including the same | |
| CN109395597A (en) | A kind of polytetrafluoroethylene (PTFE) rolled film and preparation method thereof | |
| CN105709618A (en) | Amphiphilic triblock copolymer blending-modified polyvinylidene fluoride hollow fibrous membrane | |
| WO2014142381A1 (en) | Method for manufacturing pollution-proof nanofiber separation film and pollution-proof nanofiber separation film manufactured thereby | |
| CN109395599A (en) | A kind of polytetrafluoroethyltubular tubular membrane and preparation method thereof | |
| CN109395606A (en) | A kind of polytetrafluoroethylene (PTFE) rolled film and preparation method thereof | |
| CN109395600A (en) | A kind of polytetrafluoroethyltubular tubular membrane and preparation method thereof | |
| CN109395611A (en) | A kind of polytetrafluoroethylene film and preparation method thereof | |
| CN109395605A (en) | A kind of polytetrafluoroethylene (PTFE) rolled film and preparation method thereof | |
| CN109395598A (en) | A kind of polytetrafluoroethyltubular tubular membrane and preparation method thereof | |
| CN109395604A (en) | A kind of polytetrafluoroethylhollow hollow fiber membrane and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190301 |